Fixed and portable coating apparatuses and methods

ABSTRACT

A system and method for depositing a coating may comprise a coating chemical reactor, surface activation component, and a deposition component. A target surface may be prepared for deposition with the surface activation component. The coating chemical reactor may comprise a coating chemical dispenser and a coating chemical verifier that prepares the coating chemical for deposition. The coating chemical verifier may utilize an optical excitation source and at least one optical detector, wherein chemical substances are identified by unique signatures composed of binary code. The coating chemical may be received by the deposition component to depositing the coating chemical on the target surface.

RELATED APPLICATIONS

This application is a divisional application of U.S. Non-provisionalapplication Ser. No. 14/301,643, filed on Jun. 11, 2014, which claimspriority to U.S. Provisional Patent Application No. 61/833,578, filed onJun. 11, 2013. The entirety of each of the aforementioned applicationsis incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under Grant No.DD-N000141110069 from the Office of Naval Research at the US Departmentof Defense. The government has certain rights in the invention.

FIELD OF THE INVENTION

The present invention is directed to systems and methods for depositinga coating, including deposition with an apparatus providing surfaceactivation and chemical verification.

BACKGROUND OF THE INVENTION

Materials processing and deposition of materials for the purpose ofattaining various desired properties and effects have been described.For example, thermal or e-beam evaporation may be used to depositmetal/metal alloy for electrodes or to deposit semiconductors forelectronics. The use of high vacuum allows vapor particles to traveldirectly to the target object (substrate), where they condense back to asolid state. Sputtering is process whereby atoms are ejected from asolid target material due to bombardment of the target by energeticparticles (e.g. Ar plasma). Chemical vapor deposition (CVD) andmetal-organic chemical vapor deposition (MOCVD or OMVPE or MOVPE) areother processes used to produce high-purity, high-performance solidmaterials.

However, many deposition processes (including the above processes) mayonly be capable of performing a single task and may require elaboratedequipment(s). For production of complex multi-functional coatings, suchas processing and/or depositing two or more materials, the above noteddeposition processes cannot easily be achieved, requires multiple steps,or additional complexity. Apparatuses and method for an improved coatingprocess are discussed herein. The apparatus and method may be suitablefor producing complex multi-functional coatings while maintaining itsbasic nature and portability.

SUMMARY OF THE INVENTION

In one embodiment, a coating system may comprise a coating chemicalreactor, surface activation component, and a deposition component. Atarget surface may be prepared for deposition with the surfaceactivation component. The surface activation may be achieved by reactionwith ozone, oxygen, hydrogen peroxide, halogens, other reactiveoxidizing species, or combinations thereof. The purpose is to create anenergetically reactive surface to bind molecules on the surfacecovalently. In some embodiments, the surface activation may be achievedby ozone plasma generated by intense UV light. In other embodiments,surface activation may be achieved by plasma treatment. In yet anotherembodiment, surface activation may be achieved by ozone generation usinga corona discharge, flame, or plasma.

The coating chemical reactor may comprise a coating chemical dispenserthat dispenses the chemical to be coated on a substrate and a coatingchemical verifier that prepares and controls the quality of the coatingchemical for deposition. The coating chemical verifier may utilize anoptical excitation source and at least one optical detector, whereinchemical substances are identified by unique signatures composed ofbinary code. The coating chemical may be received by the depositioncomponent to depositing the coating chemical on the target surface. Insome embodiments, the substrate may absorb a base material, such as aprimer, first in order for the coating molecules to covalently link tothe absorbent material within or on top of the substrate.

The foregoing has outlined rather broadly various features of thepresent disclosure in order that the detailed description that followsmay be better understood. Additional features and advantages of thedisclosure will be described hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present disclosure, and theadvantages thereof, reference is now made to the following descriptionsto be taken in conjunction with the accompanying drawings describingspecific embodiments of the disclosure, wherein:

FIG. 1 is an illustrative embodiment of a coating apparatus anddeposition chamber;

FIG. 2 is an illustrative embodiment of a coating apparatus and combinedsurface activation and deposition chamber;

FIG. 3 is an illustrative embodiment of a setup of a first part of acoating chemical reactor, including a coating chemical dispenser and acoating chemical verification apparatus;

FIG. 4 is a graphical illustrative embodiment of how an optical spectrummay be digitized such that a specific chemical substance may berepresented by a unique signature;

FIG. 5 is an illustrative embodiment of a process of a second part of acoating chemical reactor;

FIGS. 6A-6D are illustrative embodiments of processes for coatingchemical reactor attached to material/application specific deliverydevices;

FIGS. 7A-7B are illustrative embodiments of processes for surfaceactivation and deposition;

FIG. 8 is an illustrative embodiment of a surface activation apparatusbased on an ozone generator;

FIG. 9 is an illustrative embodiment of the motion of the treatment headwith respect to the target surface to allow for an automated system;

FIG. 10 is an illustrative embodiment of a layout of electronic controlsfor a treatment head system; and

FIGS. 11A-11D are illustrative embodiments of a mass solution treatmentsystem.

DETAILED DESCRIPTION OF THE INVENTION

Refer now to the drawings wherein depicted elements are not necessarilyshown to scale and wherein like or similar elements are designated bythe same reference numeral through the several views.

Referring to the drawings in general, it will be understood that theillustrations are for the purpose of describing particularimplementations of the disclosure and are not intended to be limitingthereto. While most of the terms used herein will be recognizable tothose of ordinary skill in the art, it should be understood that whennot explicitly defined, terms should be interpreted as adopting ameaning presently accepted by those of ordinary skill in the art.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are not restrictive of the invention, as claimed. In thisapplication, the use of the singular includes the plural, the word “a”or “an” means “at least one”, and the use of “or” means “and/or”, unlessspecifically stated otherwise. Furthermore, the use of the term“including”, as well as other forms, such as “includes” and “included”,is not limiting. Also, terms such as “element” or “component” encompassboth elements or components comprising one unit and elements orcomponents that comprise more than one unit unless specifically statedotherwise.

Improved coating systems and methods are discussed herein. The systemand method may be suitable for producing complex multi-functionalcoatings (including but not limited to hydrophobic or hydrophilic,oleophobic or oleophilic, amphiphobic or amphiphilic,anti-counterfeiting, UV-resistive, anti-reflective, anti-abrasive,flame-resistance, fire-retardant, anti-static, anti-microbial/fungal andanticorrosive, etc.) while maintaining simplicity and portability.

The coating systems and methods discussed herein may be referred to asan All-In-One (AIO) system.

The AIO systems and methods discussed herein may be used to depositvarious organic, inorganic or hybrid material systems in solid,solution, or vapor phase as coatings or the like. In some embodiments,the resulting coating may range from about 1 nm to 1 mm in thicknessonto a target surface(s). In some embodiment, the application of suchcoatings may encompass self-cleaning coatings that are hydrophobic,hydrophilic, oleophobic, oleophilic, amphiphilic, and/or amphiphobic. Insome embodiment, the application of such coatings may also be applied toanti-counterfeiting measures including but not limited to chemicalsignature tags or fluorescent/phosphorescent markers. In someembodiment, the application of such coatings may improve UV-resistiveproperties. In some embodiment, the application of such coatings mayimprove anti-reflective properties. In some embodiment, the applicationof such coatings may improve anti-abrasive properties. In someembodiment, the application of such coatings may improveflame-resistance or fire-retardant properties. In some embodiment, theapplication of such coatings may improve anti-static or electricalproperties. In some embodiment, the application of such coatings mayimprove anti-microbial/fungal properties. In some embodiment, theapplication of such coatings may improve anticorrosive properties.

FIG. 1 is an illustrative embodiment of a coating apparatus anddeposition chamber. The coating apparatus may include coating chemicalreactor (1), processing gas supply (2), surface activation apparatus(3), surface activation apparatus gas supply (4), venting or vacuumapparatus (5), heating element (6), NaOH, CaO or NaHCO₃ neutralizingfilter (7), and/or activated carbon filter (8). Various attachments andconnections are made to a deposition chamber (9). The coating chemicalreactor (1) controls the processing parameters of the coating chemicalbeing introduced into the deposition chamber (9) including but notlimited to carrier gas flow rates, coating chemical concentrations,supply line pressures, system temperatures, and/or the like.

The coating chemical reactor (1) is coupled to the deposition chamber(9) and may supply the desired chemical necessary for depositing adesired coating. The coating chemical reactor (1) may provide adispenser that precisely provides the amount of coating chemicalsnecessary for depositing the desired coating and generates reactivechemicals for the deposition process; and a chemical verifier thatprovides precise quality control and verification the coating chemicalconcentration. The processing gas supply (2) is coupled to the coatingreactor (1), heating element (6), and deposition chamber (9), and maysupply the necessary chemical(s) and/or the carrier gas to the coatingchemical reactor (1) for depositing the desired coating. The necessarychemicals and/or the carrier gas may be fed to the coating chemicalreactor (1) or to the heating element (6) and deposition chamber (9).Output from the coating chemical reactor (1) and processing gas supply(2) to the deposition chamber may be controlled by one or more valves.Nonlimiting examples of coating chemicals or processing gas may includechemicals with a general formula of fluoroalkylsilane[CF₃(CF₂)_(a)(CH₂)_(b)]_(c)SiX_(4-c) (where a=0, 1, 2, . . . to 20, b=0,1, 2, . . . to 10, c=1, 2 or 3; X=Cl, Br, I or other suitable organicleaving groups); a general formula of fluoroalkylsilane[CF₃(CF₂)_(a)(CH₂)_(b)]_(c)SiX_(4-c) (where a=0, 1, 2, . . . to 20, b=0,1, 2, . . . to 10, c=1, 2 or 3; X=Cl, Br, I or other suitable organicleaving groups); a general formula of alkylsilane[CH₃(CH₂)_(a)]_(b)SiX_(4-b) (where a=0, 1, 2, . . . to 20, b=1, 2 or 3;X=Cl, Br, I or other suitable organic leaving groups); a general formulaof alkoxyfluoroalkylsilane [CF₃(CF₂)_(a)(CH₂)_(b)]_(c)Si[alkoxy]_(4-c),(where a=0, 1, 2, . . . to 20, b=0, 1, 2, . . . to 10, c=1, 2 or 3;where the alkoxy group can be methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, or a combination thereof); and a general formula ofalkoxyalkylsilane [CH₃(CH₂)_(a)]_(b)Si[alkoxy]_(4-c) (where a=0, 1, 2, .. . to 20, b=0, 1, 2, . . . to 10, c=1, 2 or 3; where the alkoxy groupcan be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or acombination thereof). The heating element (6) is used to control thetemperature of the carrier gas. The temperature of the heating elementsmay range from about room temperature (25° C.) to 1000° C.

Surface activation apparatus (3) provides activation of a substrate, ifnecessary, to improve bonding of the coating, such as by oxidizing thesurface of the substrate. In some embodiments, the surface activationapparatus (3) may provide a chamber for receiving the substrate duringsurface activation, and the substrate may be moved to the depositionchamber (9) to deposit the desired coating after surface activation. Insome embodiments, surface activation apparatus (3) may be coupled todeposition chamber (8), surface activation apparatus gas supply (4), orboth. The surface activation apparatus gas supply (4) may be used tofeed surface activation gas for activating the surface of the substratewhen desired. Surface activation of the substrate may be achieved byreaction with ozone, oxygen, hydrogen peroxide, halogens, other reactiveoxidizing species, or combinations thereof. In some embodiments, thesurface activation apparatus gas supply (4) may also be used to feed gasfor any other process described herein. For example, surface activationapparatus gas supply (4) may also supply the carrier gas for the coatingchemicals derived from the coating chemical reactor (1). The flow of gassupplied from the surface activation apparatus gas supply (4) andsurface activation apparatus (3) to the deposition chamber (9) may becontrol with a valve. The vent or vacuum apparatus (5) coupled to thedeposition chamber (9) is used to control the environment within thedeposition chamber (9), such as by removal of unwanted gases from thedeposition chamber (9). The vent apparatus (5) may be controlled by onboard electronics. A valve between the vent apparatus (5) and depositionchamber (9) may be provided. The neutralizing filter (7) and theactivated carbon filter (8) are used to neutralize or remove any harmfulchemical by products that may be generated during the surface activationor deposition processes. In some embodiments, neutralizing filter (7)may be a filter suitable for filtering NaOH, CaO, NaHCO₃, orcombinations thereof.

The first AIO system shown in FIG. 1 may be realized as portable devicescalable to the desired application requirements, target surface area,or geometry. This device may be used in the field in any location andincorporates customizable processing parameters, such as temperaturecontrol, pressure control, and processing environment gases.

FIG. 2 is an illustrative embodiment of a coating apparatus providing acombined surface activation and deposition chamber (10). As in theembodiment discussed in FIG. 1, the coating apparatus in FIG. 2 mayinclude coating chemical reactor (1), processing gas supply (2), surfaceactivation apparatus gas supply (4), venting or vacuum apparatus (5),heating element (6), neutralizing filter (7), and/or activated carbonfilter (8), which each serve the same purpose a described previouslyabove. A combined surface activation and deposition chamber (10) may beprovides that allows both surface activation and deposition of thedesired coating to occur in the same chamber, thereby obviating the needto transfer the substrate from different chambers during surfaceactivation and deposition. Various attachments and connections, similarto the attachments and connections discussed for FIG. 1, are madebetween the combined surface activation and deposition chamber (10) andcoating chemical reactor (1), processing gas supply (2), surfaceactivation apparatus gas supply (4), and venting apparatus (5). One ormore valves may be provided between such attachments and connection toallow the connections to be opened, closed, or controlled.

In contrast to FIG. 1, components of a surface activation apparatus(e.g. FIGS. 7-10) are provide by the combined surface activation anddeposition chamber (10) in FIG. 2. If surface activation is desired,surface activation apparatus gas supply (4) may provide chemicals to thecombined surface activation and deposition chamber (10) that arenecessary for improving the bonding of the coating to the substrate. Forexample, surface activation gases may include ozone, oxygen, hydrogenperoxide, halogens, other reactive oxidizing species, or combinationsthereof. Subsequently, deposition of the desired coating may beperformed by supplying the chemicals to be coated on the substrate fromthe coating chemical reactor (1), as discussed previously above.Deposition of the desired coating may occur in the same manner discussedwith respect to FIG. 1 in the combined surface activation and depositionchamber (10) in FIG. 2. The coating chemical reactor (1) controls theprocessing parameters of the coating chemical being introduced into thecombined surface activation and deposition chamber (10) including butnot limited to carrier gas flow rates, coating chemical concentrations,supply line pressures, system temperatures, and/or the like.

The second AIO system in FIG. 2 may be realized as a fixed,semi-permanent/permanent installation scalable to the desiredapplication requirements/target surface area or geometry allowing forin-line processing of large volumes/throughput of target surfaces.

FIG. 3 is an illustrative embodiment of a setup of a first part of acoating chemical reactor, including a coating chemical dispenser and acoating chemical verification apparatus. The desired coating chemical(s)are stored in a chemical reservoir cartridge 320. The introduction ofthe coating chemicals into the deposition chamber or the combinedsurface activation and deposition chamber (e.g. FIG. 1 or 2) should be acontrolled process. This is achieved by the development of a reusablechemical reservoir cartridge 320 that may be used to supply the coatingchemical treatment solution for numerous target surfaces depending onthe target surface size. The chemical reservoir cartridge 320 isinstalled into a receptacle on the coating apparatus unit whichvalidates the correct chemical cartridge is in place for the desiredcoating application via a custom designed coating chemical verificationapparatus. A coating chemical reservoir cartridge 320 or appropriatecanister is inserted between an actuator 310 and a chemical dispenser330. A chamber 335 with two optical windows 350-1, 350-2 is placedbetween the chemical reservoir cartridge 320 and the dispenser 330 andused for the coating chemical verification. The actuator 310 controlsthe amount of chemical treatment solution that is dispensed into thecoating chemical reactor (see FIG. 5 for additional details).

The coating chemical verification apparatus is comprised of an opticalexcitation source 340 and one or more optical detectors 350-1, 350-2.While the embodiment shown a single excitation source, other embodimentsmay utilize one or more different optical heads with specific wavelengthranges of excitation sources depending on the resonant signature of eachexcitation source and response of the molecules excited. For example, insome embodiments, the number of different optical heads may be two orthree. Quality control and validation of the coating chemicals aremeasured by onboard electronics. For example, quality control andvalidation may use pixilation counting from either a CCD head or usingoptical filters and silicon detectors, examining the normalizedintensity profile and depending on relative intensity when compared toeach optical filter barrier. When activated by the insertion of achemical reservoir cartridge 320, the coating chemical verificationapparatus passes the output of the optical excitation source 340 into anoptical window 360-1 located next to the chemical reservoir cartridge.The specific molecules inside the chemical reservoir cartridge 320 areexcited by the optical excitation source 340. A specific resonancesignature is determined by the specific excitation source for thatsample. For example, samples that are excited by the UV and resultfluorescence or phosphorescence in a certain wavelength may have adifferent response when the molecules are then excited by an IR source.Specifically, when a mixture of molecules is excited simultaneously byUV and IR sources, some molecules may respond to the UV and emitfluorescence or phosphorescence in the visible of a certain wavelength,while others (anti-stokes molecules) may respond to the IR and emitfluorescence or phosphorescence in the visible but a differentwavelength. The optical detectors 350-1, 350-2 can ascertain the degreeof optical absorption and/or intensity of emitted energies from thespecific molecules through optical windows 360-1 and 360-2 located nextto the chemical reservoir cartridge 320. The optical profiles obtainedmay be normalized to the maximum value observed in order to counteractany small changes in measurement due to variations in the coatingchemical concentration. The coating chemical verification apparatuscontinuously monitors the composition of the chemical treatment solutionto ensure the quality of the chemical treatment solution, as well as toverify the presence of any contaminants or foreign chemicals. If thecomposition of the chemical treatment solution does not match with apreset signature defined by the coating chemical verification apparatus,the dispenser 330 is locked and prevents use. In some embodiments, thismay allow the coating chemical verification apparatus to adjust actuator310 to dispense chemical necessary to comply with the desired chemicalconcentration if possible. In other embodiments, chamber 335 may bevented to remove chemicals with the incorrect concentration orimpurities. Thus, this technique is applicable to a wide range ofchemical concentrations.

Magneto-optical detection is also possible where the coating chemicalverification apparatus would contain both molecules responsive tooptical detection and molecules sensitive to magnetic fields and respondto a specific magnetic field when excited. For example, this could be anamalgam of two differing materials in a composite format, but in themanner of a thin film. The correlation would work by having a specificpulse from an optical source and looking at the time resolved decay ofthe optical material and can also include a spectral examination of thefluorescence/phosphorescence. Small magnetic molecules, such as carbonnickel compounds, can be mixed with the phosphorescent/fluorescentpolymers, the resulting mixture can be excited magnetically and/orrespond to the magnetic field. Alternatively, the fluorescent/phosphormolecules can be placed on a magnetic strip containing specificinformation (acting as an active ‘smart’ substrate) where the thin filmof phosphorescent/fluorescent molecules lie on top. The magnetic film isthen pulsed to get a specific magneto response, and depending on thatresponse, the optical system will then receive information on how muchpower and specific clocking time in the decay signal should be expected.This pulsing optically is then correlated so that both signals have apredetermined result, and so that detection and consequently operationof the system is dependent on these signals.

FIG. 4 is a graphical illustrative embodiment of how an optical spectrummay be digitized such that one or more specific chemical substance(s)may be represented by a unique signature. An optical spectrum may bedigitized such that specific chemical substance(s) may be represented bya unique signature composed of binary numbers either in a matrix or in asequence of concatenated strings. The information recorded by theoptical detectors can be mapped and represented in the form of a binarycode that fully describes the particular optical profile measured. Itcan simply be defined as dividing the optical profile or typicalspectrograph into a grid pattern where the resolution is determined bythe available memory of the chip used. Any grid square having themajority of its area that is above the curve tracing the Intensity vs.the Energy (or Wavelength) measured by the optical detectors is given a‘0’. Any grid square having the majority of its area below the curvetracing the Intensity vs. the Energy (or Wavelength) measured by theoptical detectors is given a ‘1’. The grid may then be represented as amatrix having a particular number of rows and columns defined by theresolution allowable by the available memory. By comparing the measuredmatrix to a predetermined matrix corresponding the concentrationsdesired for depositing a desired coating, it is possible to verify ifthe correct chemical(s) and/or concentration(s) are being used orinserted into the coating apparatus unit.

The coating chemical reactor controls the processing parameters of thecoating chemical being introduced into the deposition chamber or thecombined surface activation and deposition chamber including but notlimited to carrier gas flow rates, coating chemical concentration,supply line pressures, system temperatures or the like.

In some embodiments, the coating chemical reactor may be attached to amaterial or application specific delivery device used to more preciselydeliver the coating chemical to a desire portion of the substrate. Thismay be achieved by implementation of an array of nozzles connected tothe coating chemical reactor. The nozzles may have apertures, in therange in size from 10⁻⁶ to 10¹ meters, for the dispersing of the coatingchemical. This arrangement allows for the coating chemical to beactively positioned or placed within dense fibers of a textile substrateto attain a deeper more uniform application. This may also be performedin conjunction with manipulation of the substrate such as bending,rolling, compressing, and tensioning with the aid of brushing rollers,cards, plates, compressed gas or other suitable aid.

For some specific substrates, a treatment of absorbent molecules(sometimes referred to as a primer) may be required for some coatingprocesses. In some embodiments, the coating systems may be designed todeliver absorbent molecules for the substrate to absorb on the surfaceor within its structure to form the primer layer. The coating moleculesmay be subsequently vapor or solution deposited onto the primer layer orthe primer/substrate interface, thereby providing a covalent linker. Theprimer molecules being absorbed may be heat-treated to form across-linked structure prior to the deposition of the coating, whichprovides a firmer linker between the substrate and the primer layer.

FIG. 5 is an illustrative embodiment of a process of a second part of acoating chemical reactor. The second part of the coating chemicalreactor may generate the reactive chemical vapor for conducting thechemical treatment in the deposition chamber or the combined surfaceactivation and deposition chamber. The coating chemical treatmentsolution, which is composed of reactive chemicals, is injected by adispenser 510 (from the coating chemical dispenser, e.g. FIG. 3) ontothe heating elements 520. Solvent may be included in the chemicaltreatment solution, such as but not limited to nonpolar aliphatic (e.g.hexanes) or aromatic (e.g. toluene) compounds, which are miscible withthe reactive chemicals. The temperature of the heating elements may havean operable range from about room temperature (25° C.) to 1000° C. Oncethe reactive chemicals are vaporized, the chemical vapor is carriedthrough to the deposition chamber or the combined surface activation anddeposition chamber by a carrier gas flow from the input 530 to output540. The carrier gas, which may be composed of the pure form or amixture of hydrogen (H₂), noble gases such as helium (He), nitrogen(N₂), oxygen (O₂), argon (Ar), halogens (e.g. F₂ and Cl₂), carbondioxide (CO₂), hydrocarbons (methane, ethane, propane and ethylene),compressed dry air (a mixture of 20% O₂ and 80% N₂), or the like. Thesurface activation may activate the target surface by reaction withozone or other reactive oxidizing species. Surface activation may alsooccur via introduction of chemical species in solvated, vapor, or solidphase such that an interaction occurs whereby the target surface issuitably modified into a reactive state. In some embodiments, surfaceactivation may be carried out via ozone generation in proximity to acorona discharge. In some embodiments, surface activation may occur insurface activation apparatus (See surface activation apparatus 3 in FIG.1). In other embodiments, surface activation may occur in a combinedsurface activation and deposition chamber (See combined surfaceactivation and deposition chamber 10 in FIG. 2).

FIGS. 6A-6D are illustrative embodiments of processes for coatingchemical reactor attached to material/application specific deliverydevices. FIG. 6A displays the use of a vapor chamber 605 aided by aconveyor roller 610 to subject a radius of curvature (ranging from about1 mm to 5 m) to the textile 615 to allow the vapor to more deeplypenetrate into the textile. Bending the textile 615 may enhance vaporaccess deeper into the material. FIG. 6B displays the vapor beingdispensed through a nozzle 620 directed at the textile 625 surface aidedby a brushing roller 630 which helps to separate out the textile fibersprior to exposure to the vapor, thereby allowing the vapor to moredeeply penetrate into the textile. FIG. 6C displays the vapor beingdispensed through a nozzle 635 directed at the textile 640 surface aidedby a compressed air nozzle 645 which helps to separate out the textilefibers prior to exposure to the vapor allowing for the vapor to moredeeply penetrate into the textile. FIG. 6D displays the textile 650being pulled over a larger radius conveyor roller 655, which subjectsthe textile to a large radius of curvatures that allows the vapor tomore deeply penetrate into the textile, and the vapor being dispensedthrough nozzles 660 directed at the textile surface aided by a brushingroller 665, which helps to separate out the textile fibers prior toexposure to the vapor allowing for the vapor to more deeply penetrateinto the textile. The rollers/conveying apparatus used to translate thetextile through the process have dimensions proportionate to the textilebeing processed.

FIGS. 7A and 7B are illustrative embodiments of processes for surfaceactivation and deposition. The chamber illustrated is an exemplaryembodiment of the deposition chamber (9) or the combined depositionchamber and surface activation apparatus (10) previously discussed withrespect to FIGS. 1 and 2. Chamber 710 may be constructed from a rigid(e.g. anodized Aluminum) or flexible material (e.g. metallized polyester‘Mylar’) including but not limited to plastics, metals, ceramics, woodor a combination thereof. The chamber 710 may serve as a depositionchamber or a combined deposition chamber and surface activation chamber.Chamber 710 may have a fixed dimension and capacity or may be adjustableto change shape and size according to the requirements of the targetsurface(s). The chamber 710 may also allow for modifications to thelocal environment inside the enclosure, such as but not limited totemperature, pressure, volume, or the like. In some embodiments, chamber710 may receive processing gases or coating chemicals as required by thespecific application.

Surface activation inside the chamber 710 may be achieved via ozoneplasma generated by intense UV light sources 720 in the vicinity of thetarget surface 730. The UV light source may incorporate a protectivehousing and shutter 740 apparatus to protect the UV light source fromthe coating chemicals. The chamber 710 may also provide an inlet 750,outlet 760, and valve 770 to allow gases to pass through the chamberwhen desired. In a surface activation phase, the chamber 710 may providespace for placing the substrates 730, UV lamps 720, a shutter 740 and acontrol valve 770. Carrier gas such as but not limited to the pure formor a mixture of hydrogen (H₂), helium (He), nitrogen (N₂), oxygen (O₂),argon (Ar), halogens (F₂ and Cl₂), carbon dioxide (CO₂), hydrocarbons(methane, ethane, propane and ethylene) or compressed dry air (a mixtureof 20% O₂ and 80% N₂) flows into the chamber 70 through the inlet 750.In order to increase the efficiency of ozone generation, UV lamps and/orsurface activation supply gas may be used. Nonlimiting examples of thesurface activation supply gas may be oxygen (O₂) or compressed dry air(a mixture of 20% O₂ and 80% N₂). The surface activation supply gas isused to generate active chemical species such as but not limited toozone and oxygen radicals. In some embodiments, during the surfaceactivation phase, a flow of surface activation supply gas passes throughthe chamber 710 while the UV lamps 720 are on with the shutter 740opened and the valve 770 closed. The active chemical species activatethe target surface to facilitate the surface chemical reactions duringthe deposition phase.

During the deposition phase shown in FIG. 7b , a carrier gas withreactive chemicals (from the coating chemical reactor e.g. FIG. 5) ispassed through the chamber 710 over the target surface 730 from theinlet 750 to outlet 760. For the purposes of illustration, such achamber 710 would be a combined surface activation and depositionchamber. In some embodiments, the surface activation chamber anddeposition chamber may be combined. In other embodiments, the surfaceactivation apparatus and deposition chamber may be separated. During thedeposition phase, the UV lamps 720 are off with the shutter closed 740and valve 770 opened. This setup prevents the reactive chemicals fromreacting with the surface of the UV lamps 730. In embodiments, with aseparated surface activation apparatus and deposition chamber, the UVlamps 730 and shutter 740 may not be present in a deposition chamber.

FIGS. 8-10 are illustrative embodiments of a surface activationapparatus. As a nonlimiting example, surface activation may be achievedvia plasma treatment, whereby plasma comprising any suitable element(s)is allowed to come into contact with the target surface (10). Surfaceactivation may be also achieved via ozone generation in proximity to acorona discharge. This may be achieved by the incorporation of themoveable treatment head that may provide a dielectric (11), topelectrode (12), bottom electrode (13), power supply (14), sensors (15),microcontroller (16), and actuator (17). Surface activation may beachieved via introduction or removal of charges due to an externallyapplied electric field (i.e. static charging bar, point source, or thelike). FIG. 8 is an illustrative embodiment of a surface activationapparatus based on an ozone generator utilizing corona discharge toproduce cold plasma. When a surface (10) is in close proximity to theelectrodes (12, 13) it is exposed to the generated ozone and cold plasmawhich is highly reactive and serves to activate the surface. In the caseof a glass surface, the bonds at the surface are broken yielding highlyreactive sites. A controlled corona discharge is obtained by placing aninsulator (or dielectric) (11) material between two electrodes (12, 13).A high frequency (equal to or between approximately 1,000-20,000 Hz),alternating current (AC) at high voltages ((equal to or betweenapproximately 1000-30000 V) is applied across the dielectric using twoelectrodes using a power supply (14). By modifying the electrodegeometries it is possible to control the direction/location of thecorona discharge such that the bottom electrode (13) is most active inthe system and as such the target substrate (10) is placed under thebottom electrode to be exposed to the corona discharge and becomeactivated. The top electrode (12) may provide of a planar flat geometry,whilst the bottom electrode provides of numerous finely spaced ((equalto or between approximately 0.1 mm-5 mm) lines ranging in width ((equalto or between approximately 0.1 mm to 1 cm) spread out across the areaspanned by the corresponding top electrode. In some embodiments, thedielectric (11) is chosen to be glass or ceramic, whereas ceramic ispreferred as it withstands localized temperature changes withoutshattering. The top and bottom electrodes (12, 13) are typically made ofa metal or metal alloy (aluminum, copper, silver, gold, stainless steel,nickel, or the like) such that it may withstand the conditions of thesystem such as a high concentration ozone environment. In order toactivate larger areas, the ozone generator can be incorporated into amoveable treatment head, such as a raster, capable of travelling acrossthe entire target surface by means of at least two directions ormovement.

FIG. 9 is an illustrative embodiment of the motion of the treatment headwith respect to the target surface to allow for an automated system. Thearrows indicate the movement of travel for the treatment head. Thetreatment head may be translated across the target surface by means ofan electronic motor attached to a system of pulleys, belts, drivingwheels, gears, any other suitable actuators, or combinations thereof.Linear actuators in the form of a gantry system may also be incorporatedfor this task. The system may also have a sensor to feedback and controlthe height of the treatment head from the surface (10) being activated.

FIG. 10 is an illustrative embodiment of a layout of electronic controlsfor a treatment head system. The movable treatment head has sensors (15)that enable it to detect when to the change direction of travel. Thesensors (15) provide feedback to the microcontroller (16) which thencomputes the next movement of the treatment head by giving theappropriate signal to the actuator (17). The sensors (15) can beoptical, electronic, mechanically based systems, or a combinationthereof. The microcontroller may be initially programmed using acomputer interface or by an attached visual basic interface, andsubsequently independently powered acting as an autonomous system.

In some embodiments, the substrates may be subjected to a solutiontreatment before coating in the coating apparatus. FIGS. 11A-11D areillustrative embodiments of such mass solution treatment systems whichare designed for, but not limited to, carpet and textile industries.FIG. 11A is an illustrative embodiment of a solution treatment systemwhere the carpet or textile 1105 is passing through a trough 1110 filledwith the treatment solution 1115. The solution 1115 is kept at a lowtemperature below the flash point of the solvents to prevent vaporbuild-up by a set of coolant rods 1120. As shown in the enlarged view inFIG. 11C, trough 1110 provides one or more coolant rods 1120. Forexample, the solution is kept below 9° C. for a solution containingethanol and other alcohols. As shown in the enlarged view of FIG. 11B,an air/gas delivery system comprised of air handlers 1125 and pipes 1130is designed to keep the interface cold and reduce the concentration ofsolvent vapor by blowing cold or inert gas (such as Nitrogen or Argon).In some embodiments, the pipes 1130 blow air at the interface where thecarpet 1105 enters the treatment solution. One or more grounded metalrollers 1135 are positioned before the carpet 1105 enters the solution1115 to prevent the potential of static electricity build-up on thesubstrate which can cause a flash.

Referring to FIG. 11D, the chamber for the solution treatment system isdesigned to contain the ‘wetting’ compartment of the substrate at a cooltemperature, but also contains a ventilation system to capture anyresidue gas vapor build-up and re-condense the vapor to solvents thatcan be added back to the supply. Carpet roll A is positioned on rollersB that direct the carpet C through the solution treatment solution intrough D. Once carpet C exits the trough D, squeeze rollers E wring anyexcess solution from the carpet. The chamber may also provide a fumehood F and ducting G to capture any residue gas vapor. Outside of thechamber ducting I may provide residue gas vapor to AC system H, whichre-condenses the vapor to solvents. Carpet intake door J allows thecarpet C to be placed into the chamber.

In general the portable coating apparatus may operate as follows:

-   -   A specific coating chemical or a combination of chemicals is        sourced. In some embodiments, the chemicals may be placed in a        coating chemical reservoir cartridge.    -   The coating chemical dispenser is set to deliver the desired        amount of material to the coating chemical reactor.    -   The target surface may be treated by a surface activation        apparatus related to one of the processes described above for        the deposition chamber (9) or the combined surface activation        and deposition chamber (10).    -   The raw carrier gas or a different venting gas may optionally be        used to prime the deposition chamber (9) or the combined surface        activation and deposition chamber (10) before the introduction        of the coating chemical.    -   For the case of a gaseous phase coating chemical application,        the coating chemical vapor is transported by a carrier gas along        the one directional supply line (e.g. highly chemically        resistant PTFE) into the desired deposition chamber (9) or the        combined surface activation and deposition chamber (10).    -   Once this process is completed, the deposition chamber (9) may        be vented again to finish the coating procedure. In the case of        combined surface activation and deposition chamber (10) it may        also be vented again to allow the removal of the target        surface(s). While the process is described in a particular order        above, in other embodiments, the order of the steps may be        varied or steps may be combined.

Experimental Example

The following examples are included to demonstrate particular aspects ofthe present disclosure. It should be appreciated by those of ordinaryskill in the art that the methods described in the examples that followmerely represent illustrative embodiments of the disclosure. Those ofordinary skill in the art should, in light of the present disclosure,appreciate that many changes can be made in the specific embodimentsdescribed and still obtain a like or similar result without departingfrom the spirit and scope of the present disclosure.

In the following example, the process demonstrates how the coatingapparatus is used to produce a coating exhibiting self-cleaningproperties on glass. However, it will be understood by those of ordinaryskill in the art that the coating apparatuses discussed herein are notspecifically limited to coating glass. A plain glass substrate is firstcleaned with soap water and washed with de-ionized water thoroughly.After drying, the glass is transferred into a combined depositionchamber and surface activation apparatus at room temperature withrelative humidity level of 16%. The glass surface is activated insidethe combined surface activation and deposition chamber via ozone plasmagenerated by intense UV light source in the vicinity of the glasssurface for 5 to 30 minutes. A solution oftrichloro(1H,1H,2H,2H-perfluorooctyl)silane in anhydrous hexane isintroduced into the coating chemical reactor through a coating chemicaldispenser and a coating chemical verification apparatus. A carrier gas(compressed air) with reactive chemicals vapor is passed through thechamber over the glass surface. After 5 to 30 minutes, the glass isremoved from the combined deposition chamber and surface activationapparatus. The treated glass is cleaned with soap water and washed withde-ionized water thoroughly. The transmission of the resulting coatingat the visible light range is expected to remain the same as pristineglass (the difference of transmission is below the errors of a commonUV-vis spectrometer). The critical angle for a 0.05 mL sessile drop ofde-ionized water to sliding down the coated surface will be ˜20°.

In the following example, the process demonstrates how the coatingapparatus is used to produce a coating exhibiting self-cleaningproperties on polished aluminum. However, it will be understood by thoseof ordinary skill in the art that the coating apparatuses discussedherein are not specifically limited to coating aluminum. A plainaluminum plate is polished first with abrasives until the surfacebecomes reflective. The polished aluminum plate is cleaned with soapwater and washed with de-ionized water thoroughly. After drying, thealuminum plate is transferred into a combined deposition chamber andsurface activation apparatus at room temperature with relative humiditylevel of 16%. The aluminum surface is activated inside the combinedsurface activation and deposition chamber via ozone plasma generated byintense UV light source in the vicinity of the glass surface for 5 to 30minutes. A solution of trichloro(1H,1H,2H,2H-perfluorooctyl)silane inanhydrous hexane is introduced into the coating chemical reactor througha coating chemical dispenser and a coating chemical verificationapparatus. A carrier gas (compressed air) with reactive chemicals vaporis passed through the chamber over the aluminum surface. After 5 to 30minutes, the aluminum plate is removed from the combined depositionchamber and surface activation apparatus. The treated aluminum plate iscleaned with soap water and washed with de-ionized water thoroughly. Thereflectivity of the resulting coating at the visible light range isexpected to remain the same as pristine aluminum (the difference ofreflectivity cannot be distinguished by common eyes). The critical anglefor a 0.05 mL sessile drop of de-ionized water to sliding down thecoated surface will be ˜20°.

While the invention described herein specifically focuses on coatingapparatus used to deposit various organic, inorganic or hybrid materialsystems in solid, solution, or vapor phase as coatings, one of ordinaryskills in the art with the benefit of this disclosure would recognizethe extension of such approaches to other systems.

Embodiments described herein are included to demonstrate particularaspects of the present disclosure. It should be appreciated by those ofskill in the art that the embodiments described herein merely representexemplary embodiments of the disclosure. Those of ordinary skill in theart should, in light of the present disclosure, appreciate that manychanges can be made in the specific embodiments described and stillobtain a like or similar result without departing from the spirit andscope of the present disclosure. From the foregoing description, one ofordinary skill in the art can easily ascertain the essentialcharacteristics of this disclosure, and without departing from thespirit and scope thereof, can make various changes and modifications toadapt the disclosure to various usages and conditions. The embodimentsdescribed hereinabove are meant to be illustrative only and should notbe taken as limiting of the scope of the disclosure.

What is claimed is:
 1. A method for depositing a coating, the methodcomprising: activating a surface of the substrate with a surfaceactivator, wherein surface activator generates ozone, oxygen, hydrogenperoxide, halogens, or other oxidizing species that render the surfaceenergetically reactive after treatment; preparing coating chemicals witha coating reactor for coating the substrate with a desired coating,wherein the coating reactor comprises a dispenser supplying the coatingchemicals and a chemical verifier validating the coating chemicals;validating the coating chemicals to ensure correct, desired chemicalsare supplied for the desired coating; coating the surface with thedesired coating, wherein the surface covalently binds with molecules ofthe coating chemicals; exciting the coating chemicals and monitoringoptical absorption or optical intensity with at least one opticaldetector; and digitizing an optical profile detected by the at least oneoptical detector into a binary code that represents the optical profileof the coating chemicals, wherein the optical profile is divided into agrid pattern, any grid squares with a majority of its area above a curveof the optical profile are assigned a “0” value, and any other gridsquares with a majority of its area below the curve are assigned a “1”value.
 2. The method of claim 1, wherein the activating and coatingsteps are both performed in a combined surface activation and depositionchamber.
 3. The method of claim 1, wherein the coating step is performedin a first chamber and the activating step is performed in a secondchamber separate from the first chamber.
 4. The method of claim 1,further comprising the step of venting during the activating or coatingstep to control an environment during the activating or coating step. 5.The method of claim 1, further comprising removing unwanted by productsduring the activating or coating step with one or more filters.
 6. Themethod of claim 1, wherein the coating chemicals have a general formulaof fluoroalkylsilane [CF₃(CF₂)_(a)(CH₂)_(b)]_(c)SiX_(4-c) (where a=0, 1,2, . . . to 20, b=0, 1, 2, . . . to 10, c=1, 2 or 3; X=Cl, Br, I orother suitable organic leaving groups); fluoroalkylsilane[CF₃(CF₂)_(a)(CH₂)_(b)]_(c)SiX_(4-c) (where a=0, 1, 2, . . . to 20, b=0,1, 2, . . . to 10, c=1, 2 or 3; X=Cl, Br, I or other suitable organicleaving groups); a general formula of alkylsilane[CH₃(CH₂)_(a)]_(b)SiX_(4-b) (where a=0, 1, 2, . . . to 20, b=1, 2 or 3;X=Cl, Br, I or other suitable organic leaving groups);alkoxyfluoroalkylsilane [CF₃(CF₂)_(a)(CH₂)_(b)]_(c)Si[alkoxy]_(4-c),(where a=0, 1, 2, . . . to 20, b=0, 1, 2, . . . to 10, c=1, 2 or 3;where the alkoxy group can be methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, or a combination thereof); or alkoxyalkylsilane[CH₃(CH₂)_(a)]_(b)Si[alkoxy]_(4-c) (where a=0, 1, 2, . . . to 20, b=0,1, 2, . . . to 10, c=1, 2 or 3; where the alkoxy group can be methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combinationthereof).
 7. The method of claim 1, further comprising comparing thebinary code to a desired code corresponding to the desired coating. 8.The method of claim 1, wherein the preparing step comprises dispensing asolvent of the coating chemicals to a heating element, wherein theheating element converts the solvent of the coating chemicals into areactive chemical vapor.
 9. The method of claim 1, further comprisingtransporting the substrate with a conveyor roller, wherein the conveyorroller subjects the substrate to a radius of curvature equal to orbetween 1 mm to 5 m during deposition.
 10. The method of claim 1,further comprising transporting the substrate with a brush roller,wherein the brush roller separates fibers of the substrate duringdeposition.
 11. The method of claim 1, further comprising supplyingcompressed air to the substrate with a compressed air nozzle, whereinthe compressed air separates fibers of the substrate during deposition.12. The method of claim 1, further comprising transporting the substratewith a conveyor roller and a brush roller, wherein the conveyor rollersubjects the substrate to bending during deposition, and the brushroller separates fibers of the substrate during deposition.
 13. Themethod of claim 1, wherein the surface activator comprises one or moreUV light sources, and the one or more UV light sources generating ozoneplasma in a vicinity of the substrate.
 14. The method of claim 1,further comprising supplying surface activation gas utilized for theactivating step.
 15. The method of claim 1, further comprising applyingan alternating current across a dielectric positioned between twoelectrodes to provide corona discharge near the substrate.
 16. Themethod of claim 1, further comprising: transporting the substratethrough a treatment solution; and controlling a temperature of thetreatment solution with coolant rods.
 17. The method of claim 16,wherein the substrate is transported with a metal roller that isgrounded.
 18. The method of claim 16, further comprising blowing coldgas at an interface of the substrate and treatment solution.